Process for molding refractory oxides



Patented Jan. 23, 1 951 PROCESS FOR MOLDING REFRACTORY OXIDES Archibald H. Ballard, Niagara Falls, Ontario, Canadaassignor, by mesne assignments, to the 7 United States of America as represented by the United States Atomic Energy Commission NoDrawing. Application February 12, 1947, Serial No. 728,198

7 Claims. (Cl. 25-156) Other objects will be in part obvious or in part pointed out hereinafter. The invention accordingly-consists in the combination of-elements and in the several steps and relation and order of each of said Steps to one or more of the others thereof all as will be illustratively described herein, and the scope of the application of which will be indicated in the following claims.

*According to )the invention I provide anyre fracto'ry' oxide 'more' refractory than silica (quartz, M. P. 1470 C.) or any combination of refractoryoxides' all of which aremore refractory than silica. The oxide or oxides should be pure, that is to say non-oxide material and/or silica and/or oxides-less refractory than silica should not be present to an extent greater than Fluxes are not desired since according to the process of this invention, no substantial amount of material in liquid phase should be present during the molding hereinafter described. Soda, potash, lime, boric oxide. phosphoric oxide and thelike are fluxes which should not be presentin total amount greater than said one per cent and preferably even less. However, pure lime is refractory andcan be used. The process of this invention involves recrystallization under pressure in contradistinction to what is commonlyv known as vitrification which. involves a fluxing, or melting of one or more of the constituent oxides. Silica (quartz) has a relatively low meltingpoint, and with other oxides forms low melting glasses. Silica has no sharp melting point. Silica can assume an amorphous state" where as the'refractory oxides which are processed according to this invention are not found in a strictly amorphous state so far as I am aware. Amorphous silica is unstable in that it can crystallize. Silica is more easily reduced than the refractory oxides that are processed according to the present invention.

Any combination of oxides should be, as a combination, more refractory than silica.- Thus while lime can be used alone, it should not be used in combination with other oxides in amounts sufficient to form-a low melting phase.

I provide a refractory mold, including one or more ,mold plungers. Preferably the mold is made of graphite which is a most satisfactory .material because it is refractory and is easily 2 ing that the mold should not be made of the same" oxide as the material to be molded; since ifthey- Were the same the latter would become' integral with the former.

"I further provide a pressure-sintering wayNo. 2125,588. In fact any type of furnace which will heat the contents of a graphite mold,

which furnace is also provided withmeans to exert pressure on the contents of the mold; may

be used;

.Lhave discovered that the objects of the in-' ventioncan be achieved if the oxide to be molded is in the form of very fine particles. that is the major portion of the material beina of ten micronsor less in particle size, and 98% of thematerial' consisting of particles none of which is larger than50 microns. The process can be carried out with practically .all of the refractory oxides above silica including the following: alumina, barium oxide, beryllia, cerium oxide,

chromic oxide, lime, if pure, ma' nesia, stron-' tium oxide, titania, thoria, uranium oxide, vanadium oxide, zirconia. Of these I have actualy tried. with successful results. the molding according to the invention of alumina, beryllia,

magnesiathoria and uranium oxide. I am confident that the others named can likewise be so mo ded.

The oxide should be of fine crystalline struc ture, without recr stallization. I prefer to use calcined material but wh ch has not been fused,

or heat treated at a te perature high enough "not exceeding about 1100 C. Uranium oxide of thefrirmula U308, which is the green or; black urano-ura'nic oxide if calc ned at too hieh a tfim'r.

peraturefis converted to the acid anhvdrideUOzf which is volatile, and therefore the calcining. teniperatureshould not exceed 1100 C. How-. ever, the temneratureshould be high enough-to driveiloff nearlyall water. waterof crystallization,

as carbon or product's of decomposition, such dioxide The following is a table of typical calcining furnace which maybe an induction furnace with pres sureplungers or a resistor tube furnace such as disclosed in the aforementioned patent. toRidg Uranium Oxide TABLE I Oxide Calcining Reaction Alumina ZAKOH);

Beryllia 2BeSO4.

Be(OH)z Calcium Oxide C3003--- Uranyl ammonium carbonate on calcination at above 300 C. produces the oxide U30 plus 002, N113, O2 and water. This oxide U308 is, when hegted in a graphite mold, reduced to U 2.

Magnesia MgCOa Thoria Th(OH)4 Such oxide powder, or mixture of such powders, is placed in a mold of graphite or other refractory material which may then be placed in'th'e furnace tube 50 of the furnace of the Ridgway Patent No. 2,125,588 (hereinafter referred to as the Bidgway furnace). The furnace plungers '136 and 173 (Eatent 2,125,588) are then placed in position as described in the patent and the electric current is turned on and the air pressure valves are'turned to apply some pressure on the .mold.

'The tube [5,0 the Ridgvvay furnace is a graphite tube. An important feature of the pres nt inv n ion is the us f relative y l w temperatures, that is several hundred degrees below the fusing point of the oxide, contrary to Ridgway lf'atent No, 3,091,559 .wherein a temere ur lqse is he melt n point of he exist: is advised. Specific examples of the preferred top'ternperature, as compared with the melting point, which should be employed. for specific xi es a e f ws? TABLE II The Highest Temperature During Molding .When articles are molded from the oxides of the characteristics and particle sizes specified herein, at temperatures which rise to the tem peratures for the various oxides as specified in Table II, homogeneous pieces of almost theoretical 'density are produced. Furthermore the surfaces of these 'articlesare free from any apparent reaction of'the oxide with the graphite of the mold, that is to say there has been noreduction even one surfac'e'layer. The art cles are not spalledeven though they have sharp dihedral, polyhedral and/or reentrant angles, and the articles can have ribs and grooves and can be made into many complicated shapes to high dimensional accuracy, i. e. as good as the mold. Because of the high density of these articles they are gas tight under a vacuum of as low as one micron of mercury. The articles are substantially'integral pieces "of the oxides 'in"multl crystanine" form with suflicient intercrystalline grow'tHso' thatthearticles have great strength] he a iie teete s it a e e iqiea r i f The actual density of articles made in accordance with the invention as compared to the published densities of the materials are as follows:

TABLE III Real Density from International Critical Tables Oxide Beryllia Magnesia- Thoria Uranium Oxide (U02) The apparatus involved in this invention, that is the mechanical details of the furnace, the electrical features of the furnace, the structure of the mold, and the structure and control of the pressure apparatus will 'all be found described in the above-mentioned U. S. patent to Ridgway, No. 2,125,588, which discloses and illustrates a graphite tube resistor type electric furnace of ood efficiency. Many furnaces just like that illustrated in that'patent are now in successful operation in the United States and in Canada. This present invention, however, is not limited to the simple mold shown in the above patent, since various shapes including crucibles, tubes, square and polygonal shapes with or Without bores and with or without ribs or grooves or flanges can be molded using the process of the present invention. 7

T e 1 of tem eratu e QY t preferred molding temperature ranges of Table II is not precluded, but no advantage lies in going to temperatures above these ranges. The use of temperatures close to'the melting point, however, will inmost cases result in red uction of the oxide and the formation of an outer. layer on the finished piece that'is of 'poor quality. In the case of magnesia, approach .to the melting point will reduce the magnesia to magnesium which will volatilize. In many other'cases the raising of the material to a temperature approaching the melting point will result in the formation of cargeneralize by saying that in noca-se should the temperature of molding rise higher than 250 c.

belowthe melting point of the bxiele involved In e ea 9i lumi a red cti n S ar a peratures not inuc above l'7 5 0 C. and 1 800? C. is the upper limit for'good results. In thecase of beryllia the'top temperature should be no higher than. 1 900? C. which "is 670 Cj'belo'w the melting point. perature above 1650"C. (1150? '0'. below the melt in point) will cause marked reduction. "Thoria will pick up nitrogen somewhere around 20009 C. Uranium oxide has'two known refractory forms, U 08 and U02. However, it matters" not which is used, because'in agraphite moldfUsos'is reused to UO2I' The danger point for U02 is around 1906} C. at which: temperature the oxide 'beg'in's to be reduced to thecarbi'deof'ui'aniuin;

I p s l v fi ei r 9 eis Qie l on ne i j t iiee ere t hare a c In the case of magnesia'a temiqthe p s o h fmo dseb i ls t iss great dimensional accuracy.;-To do this, account has to be talgen of the coefficients'ofexpansionof the graphite and ofthe oxide material,;which is given inthe following table;

E VW Coefii cz'ent of expansion,all figuresxlo per de' gree Centigrade, all figure; approximate" AGood 2150 an verage ver Oxide Ooefficlent Temperature Range Below Alumina. I Beryllia 7.' 8 Graphite". 3r7 ;.-4, Magnesia- 11.0 Thoria 10. 3 20-1, 400 UraniumOx e, U0 About H j :1,"70 0 I are top pressures and the pressure should gradually rise thereto. The use of low pressures necessitates the use of more time and the most prac tical thing to do is to provide agraphite mold of adequate strength and then use the indicated pressure of 1500 pounds per square inch which I believe to be satisfactory for all of the oxides more refractory than silica (quartz).

It will thus be seen, that there has been provided by this invention, a process for the molding of very dense, homogeneous refractory articles of oxides more refractory than silica in which the various objects hereinbefore given together with many thoroughly practical advantages are successfully achieved. As various other embodiments might be made of the above invention, and as the art herein described might be varied in various parts, all without departing from the scope of the present invention, it is to be understood that all matter hereinbefore set forth is to be interpreted as illustrative and not in a limiting sense.

I claim:

1. Process of molding a homogeneous, dense, integral article of beryllia which comprises providing a refractory mold including a hollow mold body and at least one mold plunger, providing a powder of beryllia of fine crystalline structure which has been obtained bycalcination at a temperature below 1100 C. and which has not been recrystallized, the major portion of which is of particle size not greater than ten microns and 98% of which consists of particles none of which is larger than 50 microns particle size, placing said powder in said mold and said mold in a furnace having pressure apparatus, and heating while pressing to a temperature and pressure which rise to between about 1650 C. and 1900 C. and at least about 500 lbs. per square inch. 1

2. Process of molding a homogeneous, dense, integral article of thoria which comprises providing a refractory mold includinga hollow mold body and at least one mold plunger, providing a powder of-thoria,of fine crystalline structure which has been obtained by calcination at a ternperature below 1100 C. and which hasnot been recrystallized, .the major portion of which is of particle size not greater than-ten, microns and 98% of which consists ofjparticles none of which is larger than 50 microns particle size, placing said powder in said mold and saidmold in a furnace having pressure apparatus; and heating while pressing to a; temperature and pressure which rise to betweenabout 1400 Grand 2000 Czandat least about 500 lbs. per square inch. H

'3. The process of molding a homogeneous dense, integral article of uranium oxide which comprises providing a refractory mold-including a hollowmold body and at least one mold plunger, providing a powder ofuranium oxide of fine crystalline structure which has been obtained calcination at a temperature belowv 1100 Cand which has not been recrystallized; the major portion of which is of particle size not greater than ten microns and 98% of which consists of particles none of which is larger than 50 microns particle size, placing said powder in said mold and said mold in a furnace having pressure apparatus, and heating while pressing to a temperature and pressure which rise to between about 1500 C. and 1900 C. and at least about 500 lbs. per square inch.

4. The process of molding a homogeneous, dense, integral article of an oxide having a melting point of at least about 1850 C. or mixture of such oxides except with lime which comprises providing a refractory mold including a hollow mold body and at least one mold plunger, providing a powder of the refractory oxide material of fine crystalline structure which has been obtained by calcination at a temperature below,

1250 C. and which has not been recrystallized, the major portion of which is of particle size not greater than ten microns and 98% of which consists of particles none of which is larger than 50 microns particle size, placing said powder in said mold and said mold in a furnace with pressure apparatus, andheating while pressing to a temperature and pressure which rise to at least 1250 C. and not higher than 250 C. below the melting point of the oxide or combination of oxides and at least about 500 lbs. per square inch.

5. The process of molding a homogeneous, dense, integral article of oxide selected from the group consisting of alumina, barium oxide, beryllia, cerium oxide, chromic oxide, pure lime, magnesia, strontium oxide, titania, thoria, uranium oxide, vanadium oxide, zirconia and mixtures thereof except with lime, which comprises providing a refractory mold including a hollow mold body and at least one mold plunger, providing a powder of the refractory oxide material of fine crystalline structure which has been obtained 7 by calcination at a temperature below 1250 C. and which has not been recrystallized, the major portion of which is of particle size not greater than ten microns and 98% of which consists of particles none of which is larger than 50 mi- 7M hollow. mold body and at least one mold plunger, providing a powder of magnesia of fine crystalline'structure which ha's'be'en obtained by cal cin'ation'at a temperature less than 1100 C. and

whichlias not been recrystallized the major portion of which is of particle size not greater than lOmicro'ns and 98% of which consists of particles none of which is larger than 50 microns particle size, placing said powder in said mold and said nioldfin a furnace having pressure apparatus, and heating while pressing to' a temperature and pressure Which rise to between about12'50 C. and 1650 0. and at least about 500 pounds per square inch.

'7. The process of molding a homogeneous, dense, integral article of alumina which comprises providing a refractory mold including a hollow mold body and at least one mold plunger, providing a powder of alumina of fine crystalline structure which has been obtained by calcination 20 2,091,569

at a temperature below 1200 C. and which has not been recrystallized, the major portion of which is of particle size not greater than 10 mie crons and 985% of which consists of particles none of which islarger than 50 microns'particle size,

B FEBENC S C D The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Ridgway et al Aug. 31, 1937 Number 

3. THE PROCESS OF MOLDING A HOMOGENEOUS, DENSE, INTEGRAL ARTICLE OF URANIUM OXIDE WHICH COMPRISES PROVIDING A REFRACTORY MOLD INCLUDING A HOLLOW MOLD BODY AND AT LEAST ONE MOLD PLUNGER, PROVIDING A POWDER OF URANIUM OXIDE OF FINE CRYSTALLINE STRUCTURE WHICH HAS BEEN OBTAINED BY CALCINATION AT A TEMPERATURE BELOW 1100* C. AND WHICH HAS NOT BEEN RECRYSTALLIZED, THE MAJOR PORTION OF WHICH IS OF PARTICLE SIZE NOT GREATER THAN TEN MICRONS AND 98% OF WHICH CONSISTTS OF PARTICLES NONE OF WHICH IS LARGER THAN 50 MICRONS PARTICLE SIZE, PLACING SAID POWDER IN SAID MOLD AND SAID MOLD IN A FURNACE HAVING PRESSURE APPARATUS, AND HEATING WHILE PRESSING TO A TEMPERATURE AND PRESSURE WHICH RISE TO BETWEEN ABOUT 1500* C. AND 1900* C. AND AT LEAST ABOUT 500 LBS. PER SQUARE INCH. 